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Petrographic Study of Beočin Zeolite Tuff

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Petrographic Study of Beočin Zeolite Tuff Proceedings of the 5th Serbian-Croatian-Slovenian Symposium on Zeolites PETROGRAPHIC STUDY OF BEOČIN ZEOLITE TUFF Vladimir Simić1, Nevena Andrić1, Vladica Cvetković1, Nikola Vuković1, Jelena Živanović2 1University of Belgrade – Faculty of Mining and Geology, Đušina 7, 11000 Belgrade, Serbia 2Avala Resources Ltd., Zeleni bulevar27/1, 19210 Bor, Serbia e-mail:[email protected] ABSTRACT Zeolite tuff in the Općište deposit has been subdivided into several varieties: medium- to coarse-grained, medium-grained and fine-grained zeolite-rich tuff, as well as medium- grained and very fine-grained to fine-grained glass-rich zeolite tuff. Zeolite-rich and glass- rich zeolite tuff varieties were already distinguished based on CEC values (> or <130 meq/100g respectively). Generally, very fine-grained to fine-grained tuff has lower, while medium-grained tuff has more zeolite content. Clinoptilolite is the dominant zeolite mineral. Keywords: zeolite, tuff, SEM, Beočin, clinoptilolite INTRODUCTION Due to their industrial significance zeolite tuffs were subject of many studies in Serbia [1-7]. All known tuff deposits in sedimentary basins in Serbia are related to Miocene volcanic activity.One of the most significant from the economic point of view is Općište zeolite. The Općište deposit is located near the Beočin Monastery, on the northern slopes of Fruška Gora. The zeolitized tuff is interstratified within Badenian marine marlstones. It occurs as one composite layer 8-25 m thick (~ 17 m in average). Overburden is 2-28 m thick, around 5.4 m in average [8]. The whole sedimentary series dips to the NNW at the angle of 15-25o. Previous exploration revealed three varieties of tuff: zeolite tuff, glass-rich zeolite tuff and glass-rich tuff (note that 'tuff' is here used in a non-genetic sense meaning that it delineates fine-grained material with volcanogenic particles irrespectively their fragmentation and depositional mechanism; see [9]). Total resources of all tuff varieties are ~2 Mt [9]. However, in 2006 only a part of the deposit with zeolitized tuff was explored in detail, and the measured and indicated resources were estimated at 364,000 t of zeolite tuff and 245,000 t of glass-rich zeolite tuff [10]. The aim of this study is petrographic characterization of zeolitic tuff in the Općište deposit. SAMPLES AND METHODS Eleven core samples of zeolite tuff from 4 boreholes drilled in 2006 have been collected. Samples were chosen in such a way to represent the vertical changes in tuff petrography. The petrographic study included optical and scanning electron microscopy. Scanning electron microscopy was used for imaging and collecting chemical data using a Jeol JSM – 6610 LV Scanning Electron Microscope fitted with energy-dispersive spectrometer (EDS). Analyses were run at an accelerating voltage of 20 kV, and working distance of 10 mm. Samples were pre-coated using the evaporated gold coating method to make the samples conductive. For quantitative chemical analysis, the microscope was calibrated for major elements using orthoclase (K), albite (Na), wollastonite (Ca), almandine (Si, Fe), MgF2 (F), Ti 1 (Ti), GaP (P) and oxides (MgO, Al2O3) as standards. RESULTS AND DISCUSSION Tuff in Općište deposit is underlain by dark grey marlstone of Badenian age. Typical cross-section through the tuff sequence (bottom to top direction) is as follows: - Marly tuff 0.6 m thick has been observed in one borehole; 104 Proceedings of the 5th Serbian-Croatian-Slovenian Symposium on Zeolites - Economically important tuff sequence starts with medium- to coarse-grained zeolite tuff 1.0- 1.6 m thick; - Medium-grained zeolite tuff, occasionally with visible biotite flakes, occurs in all positive boreholes with thickness from 0.6 to 8.8 m; - Fine-grained zeolite tuff 2.1- 8.5 m thick is the last one in zeolite-rich tuff variety; - Medium-grained glass-rich zeolite tuff 1.3 to 3.0 m thick has been detected in several boreholes; - Fine-grained to very fine- grained glass-rich zeolite tuff 1.0-16.0 m thick, is the most important variety of glass-rich zeolite tuff; - Fine-grained zeolite tuff 2 m thick was observed in only one borehole so far; - Tuff sequence finish with fragmented marly and clayey tuff. Tuff is overlain by light grey Badenian marlstone 0.7- 17.0 m thick, Quaternary loess up to 10 m thick, debris with clay up to 1.7 m thick, and soil up to 0.5 m thick. Figure 1. Log of the B-XI/06 borehole with the position of studied samples (black circles), modified after [10] Microscopic study revealed that altered volcanic glass (including zeolite minerals) predominantly occurs as glass shards. Detritus is made of phenocrysts and, rarely, larger pumice fragments. Quartz occurs as irregular angular grains, rarely in bipyramidal forms. Feldspars, represented mostly by sodic plagioclase, also occur as irregular grains with polysynthetic twinning lamellae. Biotite appears in the form of elongated flakes and is the most abundant mafic mineral, while amphiboles (hornblende) are quite rare. Carbonate minerals occasionally occur. Dimensions of mineral fragments vary according to the variety of tuff and, generally, become smaller upwards, which was also observed at outcrops in the open pit. Studied tuffs have either vitroclastic or vitrocrystalloclastic texture. In medium- 105 Proceedings of the 5th Serbian-Croatian-Slovenian Symposium on Zeolites grained tuff fossils were detected, indicating sedimentation in aqueous environment. Although the tuff is in general very pure, almost without any alochemic material, large cobbles and boulders of siltstone and fine-grained sandstone indicate a temporary input of terrigenous material into the basin. Figure 2.Fine-grained zeolite tuff – typical texture formed by abundant glass shards in the matrix (Beo-8, ppl) - left; medium-grained zeolite tuff with fragments of quartz and plagioclase phenocrysts and fossil set in glassy matrix (Beo-9, xpl) -right. ccording to SEM study, clinoptilolite is the dominant zeolite mineral. It differs in shape and grain size, from ~1μm flakes to ~5x7 μm tabular crystals (Fig. 3). Medium-grained tuff occasionally contains calcite. Glass shard relics are usually visible, displaying evidence of the initial stage of formation of clay and/or zeolite minerals (Fig. 3 C). a b c d Figure 3. a) Typical texture of fine-grained clinoptilolite tuff (Beo-6); b) Different grain shape and size of clinoptilolite in fine-grained tuff (Beo-7); c) Clinoptilolite (cpt) formed by alteration of volcanic glass (Beo-6); d) Large calcite crystals in medium-grained tuff; calcite is associated with clinoptilolite (Beo-9). CONCLUSION 106 Proceedings of the 5th Serbian-Croatian-Slovenian Symposium on Zeolites The Općište deposit is located near the Beočin Monastery, on the northern slopes of Fruška Gora. The zeolitized tuff is interstratified within Badenian marine marlstones. It occurs as one composite layer 8-25 m thick (~ 17 m in average).Eleven core samples of zeolite from 4 boreholes were studied by optical and scanning electron microscopy. Tuff in the Općište deposit is underlain by dark grey marlstone of Badenian age. Typical cross-section through the tuff sequence (bottom to top direction) is as follows: marly tuff 0.6 m thick is the transition between marlstone and high-quality zeolite tuff. Economically important tuff sequence starts with medium- to coarse-grained zeolite tuff 1.0-1.6 m thick, followed by medium-grained zeolite tuff, occasionally with visible biotite flakes, with thickness from 0.6 to 8.8 m. Fine-grained zeolite tuff 2.1-8.5 m thick is the last one in zeolite- rich tuff variety. The lower quality tuff section starts either (but rarely) with medium-grained glass-rich zeolite tuff 1.3 to 3.0 m thick, or (usually) with fine-grained to very fine-grained glass-rich zeolite tuff 1.0-16.0 m thick. Over glass-rich zeolite tuff in only one borehole fine- grained zeolite-rich tuff 2 m thick was observed. The tuff section finishes with fragmented marly and clayey tuff. Zeolite rich and glass-rich zeolite tuff varieties were distinguished based on CEC values over 130 meq/100g for zeolite-rich tuff [10]. ACKNOWLEDGEMENT This research was partly financed by the Ministry of Education and Science of the Republic of Serbia (Projects number 176006, 176016 and 176019). We are also obliged to Alas Rakovac a.d. for their kind permission to use unpublished data and results. REFERENCES [1] D. Stojanović, “Vulkanski tufovi i sedimentne stene u Srbiji sa sadržajem zeolita” in: Zapisnici srpskog geološkog društva za 1968. godinu”, Beograd, 1968, 9-20. [2] D. Nikolić, M. Terzić, and V. Poharc, “Mineraloško-hemijsko proučavanje tufova okoline Beočina na Fruškoj Gori: in: “Zbornik radova Simpozijuma "Cementna industrija", Novi Sad – Beočin”, 1975, 27-32. [3] J. Obradović, “The review on the occurrences of zeolites in sedimentary rocks in Yugoslavia” in: “Geol. Anali Balk. Pol. XLI”, Beograd, 1977, 293-302. [4] J. Obradović ,“Occurrences and genesis of sedimentary zeolites in Serbia, Yugoslavia” in: “Occurrence, Properties and Utilisation of Natural Zeolites”, D. Kallo and H.S. Sherry (Eds.), Akademiai Kiado, Budapest, 1988, 59-69. [5] V. Cvetković, V. Žumberković, K. Resimić, and O. Popov, “Miocenski piroklasti severne Bačke” in: “Zbornik radova 13. Kongresa geologa Jugoslavije, knjiga III”, Herceg Novi, 1988, 187-194. [6] V. Simić, “Pucolanski tufovi Srbije” in: “Zbornik radova međunarodnog savetovanja "Cement '99", Novi Sad – Beočin”, 1999, 164-170. [7] V. Simić, V. Cvetković, S. Đurić, and M. Kostić, “Zeolitski tuf iz okoline sela Lužnica (Šumadija)” in: “Mineralogija, II, 2”, Beograd, 39-41. [8] G. Čongradac, “Elaborat o rezervama tufova ležišta "Beočin-Manastir"”, Fond Geološkog instituta Srbije, Beograd, 1986. [9] R.A.F. Cas and J.V. Wright, Volcanic Successions: Modern and Ancient, Allen and Unwin, London, 1987. [10] S. Mojić and V. Kovačević, “Elaborat o rezervama zeolitisanog tufa i tufa sa zeolitom u ležištu "Općište" kod Beočina”, Fond Geološkog instituta Srbije, 2007.
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